3,5-Ditert.butyl-4-(N-benzoylcarbamyloxy)-benzylidenemalononitrile

ABSTRACT

N-benzoylcarbamyloxy-, chlorophenylcarbamyloxy and bromophenylcarbamyloxy-3,5-ditert.butylbenzylidene-malononitriles are useful in combating a variety of agricultural mites and insect pests, including tobacco budworm, Southern army worm, fall army worm, 2-spotted mite and European corn borer. Particularly useful against tobacco budworm are the 4-bromo-3chlorophenylcarbamyloxy- and the 2,4-dichlorophenylcarbamyloxy compounds. For control of European corn borer the Nbenzoylcarbamyloxy-, 4-bromo-3-chlorophenylcarbamyloxy- and the 2,4-dichlorophenylcarbamyloxy- compounds are particularly useful. For control of fall army worm the N-benzoylcarbamyloxy- compound is preferred.

O Unlted States Patent 1 [111 3,869,497 Cahoy et al. Mar. 4, 1975 [54]3,5-DITERT BUTYL-4-(N- 3,694,483 9/1972 Cahoy et ul 260/465 DBENZOYLCARBAMYLOXY)- BENZYLIDENEMALONONITRILE Primary Examiner-Joseph P.Brust [75] Inventors: Roger P. Cahoy, Overland Park; 4

John Sanjean, Leawood, both of Kans.

[57] ABSTRACT [73] Assignee: Gulf Research & Development Company,Pittsburgh, Pa. N-benzoylcarbamyloxy-, chlorophenylcarbamylox d b h l bl 3 5 d' b lb l' an romop eny car amy oxyltert. uty enzy [22] Filed 1973denemalononitriles are useful in combating a variety [21] Appl. No.:393,535 of agricultural mites and insect pests, including tobaccobudworm, Southern army worm, fall army .HRelated ltpphcamnlnata orm,2-spotted mite and European corn borer. Par- [60] g z g g :P' 23tlcularly useful against tobacco budworm are the 4- Bacon mua lon'm'parbromo-3-chlorophenylcarbamyloxyand the 2,4- Sept 1970'dichlorophenylcarbamyloxy compounds. For control of European corn borerthe N-benzoylcarbamyloxy-, 260/465C37,c4i2t/l3/% 4 bromo 3Ch|0r0phenylcarbamyloxy and the 24. dichlorophenylcarbamyloxy Compoundsare particw Field of Search 260/465 D, 424/304 larly useful. For Controlof fan y worm the [56] References Cited zoylcarbamyloxycompound ispreferred.

UNITED STATES PATENTS 1 Claim N0 Drawings 3.527.785 9/1970 Ozaki et a]260/465 D 1 3,5-DITERT,BUTYL-4-(N- BENZOYLCARBAMYLOXY)-BENZYLIDENEMALONONITRILE This application is a division of U.S. Ser. No.236,341 filed Mar. 20, 1972, now U.S. Pat. No. 3,825,663, which is acontinuation-in-part ofU.S. Ser. No. 70,529 filed Sept. 8, 1970, nowU.S. Pat. No. 3,694,483, which is incorporated herein by reference.

DESCRIPTION OF THE INVENTION The prior patent was directed to a group ofcarbamyloxyditert.butylbenzylidenemalononitrile insecticides havingimproved safety with respect to warm-blooded animals and a method ofcombating Southern corn rootworm with these new insecticides. It has nowbeen discovered that a small group of carbamyloxymalononitriles hasinteresting utility, particularly for the control of tobacco budworm, apest which presents a particularly difficult problem. The3-bromophenyl-, 4-bromophenyl-3-chlorophenyland 2,4-dichlorophenylcarbamyloxy compounds are particularly preferred for thispurpose.

SYNTHESIS OF THE INSECTICIDES The novel insecticides of this inventionmay be synthesized by use ofa general procedure chosen from one of thosewhich are exemplified specifically below: Preparation of3,5-ditert.butyl-4-(N- benzoylcarbamyloxy)benzylidenemalononitrile Areaction flask was charged with 13.8 g (0.049 mole) of 3,5-ditert.butyl-4- hydroxybenzylidenemalononitrile, 150 ml benzene, 7.4g (0.05 mole) of benzoyl isocyanate and a catalytic quantity ofl,4-diazabicyclo[2.2.2] octane. The reaction solution was allowed tostir overnight at ambient temperature. On the following morning, theprecipitated white-solid material was collected on a vacuum filter andwashed with hexane. The compound melted at l55-58C.

Anal. Calcd. for C H N O C, 72.70; H, 6.34; N, 9.78 Found: C, 71.71; H,6.26; N, 9.77

Preparation of 3,5-ditert.buty1-4-(2,4-dichlorophenylcarbamyloxy)benzylidenemalononitrile The required2,4-dichlorophenyl isocyanate was prepared by the dropwise addition of40 g (0.25 mole) of 2,4-dichloroaniline in 200 ml of benzene to astirred solution of 650 ml of benzene containing 12.5 weight percentphosgene. The mixture was allowed to stir overnight at ambienttemperature. On the following morning, the reaction mixture was refluxedfor 4 hours. The reaction solution was evaporated under reducedpressure. The solid residue was recrystallized from benzene-hexane andcollected on a vacuum filter under a nitrogen atmosphere. The compoundmelted at 5758C. A reaction flask was charged with 8.5 g (0.03 mole) of3,5-ditert.butyl-4- hydroxybenzylidenemalononitrile, ml of heptane, 7.0g (0.037 mole) of 2,4-dichlorophenyl isocyanate and one drop oftriethylamine. The stirred reaction mixture was heated at 50C for 30minutes and cooled. The precipitated white solid was collected on avacuum filter and recrystallized from benzene-hexane. The purifiedcompound melted at 130-l3lC.

Anal. Calcd. for C H Cl N O C, 63.83; H, 5.36; N, 8.93 Found: C, 63.52;H, 5.30; N, 9.19

USE OF THE PESTICIDES The effectiveness of the pesticides in use may bemeasured by means of the test procedures described below:

Ant/zonomus grandis boll weevil Contact Spray Test Cages containing ten2- or 3-day-old laboratoryreared adult boll weevils are exposed in ahorizontal wind tunnel to sprays of 5 ml of acetone solution of thecandidate material. Various concentrations up to 0.25% are used to givea range of kills. Four replicates are used to reduce error. Percentmoribund and dead is recorded after 24 and 48 hours. Guthion is used asthe standard.

Terranychus urticae two-spotted spider mite Spray Test Cotton seedlingsinfested (20 or more per plant) with two-spotted spider mites areexposed on a turntable in a wind tunnel to sprays of 5 m1 of an acetonesolution of the candidate material. Various concentrations up to 0.25%are used to give a range of kills. Each treatment is replicated 4 timesto reduce error. Mortality is re corded after 72 hours. Malathion isused as the standard. Systemic Test Cotton seedlings are placed in plantnutrient solution containing various concentrations of the candidatematerial. Three days later seedlings are infested (20 or more per plant)with two-spotted spider mites. Mortality is recorded 48 hours after theseedlings are infested. Each treatment is replicated 4 times. Demeton isused as the standard.

Spodoptera efridania southern armyworm Spray Test Each side of a cottonleaf is sprayed in a Potter Tower with 5 ml of acetone solution of thecandidate material. After spraying, the leaf is cut in half and eachhalf exposed in a petri dish to 10 fourth-instar larvae. Variousconcentrations up to 0.25% are used to give a range of kills. Moribundand dead larvae are recorded after 24 and 48 hours. Each treatment isreplicated 4 times. Methyl parathion is used as the standard.

Spodoptera frugiperda fall armyworm Spray Test Same method as southernarmyworm, except thirdinstar larvae are used and only 5 per petri dish.Each cotton leaf is cut in four equal parts.

Heliothis virescens tobacco budworm Same method as fall armyworm.

Laboratory Screening of Crop Protection Chemicals on the European CornBorer Candidate compounds are compared by confining 7-day-old Europeancorn borer larvae on an artificial medium that has been treated with thecandidate compound.

The media treated with candidate compounds are prepared by dissolving mgof the active compound in 10 ml of acetone containing 10 mg of Triton X-emulsifier. Ninety ml of distilled water is then added to theemulsifiable concentrate, yielding a 1,000 ppm dilution of the activechemical. The desired concentrations are then serially diluted from the1,000 ppm soluand mortality counts are made after 72 hr and percenttion.Each cup receives 0.2 ml of the dilution. age mortality is thendetermined.

Plastic jelly cups 18 mm deep X 26 mm bottom diam X 34 mm top diam) areused for test containers. An au- The rating of the best results is doneas follows: tomatic pipette is used to apply the solution on the sur- A76 100% dead adults face of the artificial medium. Five 7-day-old larvaeare B 51 dead adults introduced into each cup and confined by means of aC 26 50% dead adults paper-board cap lined with Saran. Each treatment isD l 25% dead adults replicated 4 times and all treatments are held at FE no dead adults Two- European Concn. Tobacco Southern Fall Spotted BollCorn Compound pm) Budworm Armxworm Armxworrn mite Eeevil Borer 2500 A AA A c 0 51 /CN 1000 A B A A I n A bun-c-o u=c 500 n B A A A cu 250 A 125A A 0 A c 62.5 A 31. 3 B 10 D (31 2500 A A A A 0 1000 A A A A A 500 A cA A A R 250 A Brun-c-ocn=c A 100 B c E C1 2500 A A A c 1000 A A A A cn500 A B A A nngo cn=c 250 1a A-B A 0 \CN 125 0 A-c A 100 n D B 62.5 B-CA L0 31. 3 D B 10 E 18.4 to 34.9 (Av. 26.6) mg/kg Br 2500 A A A c c 1000A B A 0 /CN 500 B c A Na-" -0 cu=c 250 \CN 125 10 Comparison Standards2500 A A A A D 1000 A A A A A 500 A A B A A 250 A noca=c \CN 125 A 100 cc B A 62. 5 A 50 31.3 A 6.5-28 (Av. 17. 2) mg/kg 1 500 A-A A-A A-AMethyl Parathion 100 A-B A-A Continued Two- European Concn. TobaccoSouthern Fall Spotted Boll Corn Compound (ppm) Budworm Arm yorm Armzwormmite tie evil Borer 2500 I A-A 1000 B-B Malathion 125 V 100 D-D 2500 C-C1000 D-C 500 r D-C Guthion 250 125 100 DDT 2500 As indicated by thetabulated table, the novel commulated as liquid spray mixtures accordingto convenpounds of this invention possess high toxicity particutionaltechniques and are applied to the plants at interlarly to tobaccobudworm and European corn borer vals during the growing season. whilepossessing a better margin of safety with respect I claim: to toxicityto warm-blooded animals than the prior art l.3,5-ditert.butyl-4-(N-benzoylcarbamyloxy)-3,5-ditert.butyl-4-hydroxybenzylidenemalononitrile.benzylidenemalononitrile.

In the typical method of use, the insecticides are for-

1. 3,5-DITERT.BUTYL-4-(N-BENZOYLCARBAMYLOXY)BENZYLIDENEMALONONITRILE.